WO2020246521A1 - 非水電解液 - Google Patents

非水電解液 Download PDF

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Publication number
WO2020246521A1
WO2020246521A1 PCT/JP2020/022013 JP2020022013W WO2020246521A1 WO 2020246521 A1 WO2020246521 A1 WO 2020246521A1 JP 2020022013 W JP2020022013 W JP 2020022013W WO 2020246521 A1 WO2020246521 A1 WO 2020246521A1
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Prior art keywords
group
lithium
aqueous electrolyte
aqueous
borate
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PCT/JP2020/022013
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English (en)
French (fr)
Japanese (ja)
Inventor
幹弘 高橋
孝敬 森中
渉 河端
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セントラル硝子株式会社
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Application filed by セントラル硝子株式会社 filed Critical セントラル硝子株式会社
Priority to JP2021524886A priority Critical patent/JPWO2020246521A1/ja
Priority to CN202080040945.XA priority patent/CN113924677A/zh
Priority to KR1020217039602A priority patent/KR20220016852A/ko
Priority to US17/596,177 priority patent/US20220231338A1/en
Priority to EP20817762.6A priority patent/EP3965204A1/en
Publication of WO2020246521A1 publication Critical patent/WO2020246521A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This disclosure relates to a non-aqueous electrolyte solution.
  • batteries which are electrochemical devices, information-related equipment and communication equipment, that is, power storage systems for small and high energy density applications such as personal computers, video cameras, digital cameras, mobile phones, and smartphones, electric vehicles, and hybrid vehicles.
  • Fuel cell vehicle auxiliary power supply, power storage system for large-scale, power applications such as power storage are attracting attention.
  • non-aqueous electrolyte batteries such as lithium-ion batteries, which have high energy density and voltage and high capacity, and are currently being actively researched and developed.
  • Non-aqueous electrolyte solution examples of the non-aqueous electrolyte solution used in the battery include lithium hexafluorophosphate (hereinafter, also referred to as “LiPF 6 ”) as a solute in a solvent such as cyclic carbonate, chain carbonate, and ester, and bis (hereinafter, also referred to as “LiPF 6 ”).
  • LiPF 6 lithium hexafluorophosphate
  • LiPF 6 bis
  • the negative electrode and the lithium cation, or the negative electrode and the electrolytic solution solvent react, and lithium oxide, lithium carbonate, or alkylcarbonate is formed on the surface of the negative electrode.
  • a film containing lithium as the main component is formed.
  • the film on the surface of the electrode is called Solid Electrolyte Interface (SEI), and its properties have a great influence on the battery performance, such as suppressing further reduction decomposition of the solvent and suppressing deterioration of the battery performance.
  • SEI Solid Electrolyte Interface
  • a film of decomposition products is formed on the surface of the positive electrode, which is also known to play an important role in suppressing oxidative decomposition of the solvent and suppressing gas generation inside the battery.
  • Patent Document 1 describes an electrolytic solution containing a silicon compound having a specific structure.
  • the present disclosure has been made in view of the above circumstances, and balances the effect of reducing the absolute value of the internal resistance at a low temperature (0 ° C. or lower, for example, ⁇ 20 ° C.) and the effect of improving the battery capacity after the cycle test. It is an object of the present invention to provide a non-aqueous electrolyte solution that can be exhibited well.
  • Non-aqueous electrolyte solution Contains non-aqueous organic solvent, solute, silicon compound (A), borate (B) and imide salt (C)
  • the silicon compound (A) is a compound represented by the following general formula (1).
  • the borate (B) is at least selected from the group consisting of at least one cation selected from the group consisting of alkali metal cations and alkaline earth metal cations, and tetrafluoroborate anion and difluorooxalatoborate anion. It is a borate consisting of a pair with one kind of anion.
  • the imide salt (C) is an imide salt represented by the following general formula (2).
  • R 1 to R 3 are substituents having at least one unsaturated bond and an aromatic ring, respectively, and at least one of R 1 to R 3 is a substituent having an aromatic ring. Is. ]
  • Rf 1 and Rf 2 independently represent a fluorine atom or a linear perfluoroalkyl group having 1 to 4 carbon atoms or a branched chain perfluoroalkyl group having 3 to 4 carbon atoms, and M + represents an alkali metal cation.
  • R 1 to R 3 are independently selected from the group consisting of an alkenyl group, an alkynyl group, an aryl group, an alkenyloxy group, an alkynyloxy group, and an aryloxy group.
  • the alkenyl group is a group selected from an ethenyl group and a 2-propenyl group.
  • the alkynyl group is an ethynyl group and
  • the aryl group is a group selected from a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 4-fluorophenyl group, a 4-tert-butylphenyl group, and a 4-tert-amylphenyl group.
  • the alkenyloxy group is a group selected from a vinyloxy group and a 2-propenyloxy group.
  • the alkynyloxy group is a propargyloxy group
  • the aryloxy group is a group selected from a phenoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, a 4-fluorophenoxy group, a 4-tert-butylphenoxy group, and a 4-tert-amylphenoxy group.
  • ⁇ 4> The non-aqueous electrolytic solution according to ⁇ 1>, wherein at least one of R 1 to R 3 is a group selected from the group consisting of an alkenyl group, an alkynyl group, an alkenyloxy group, and an alkynyloxy group.
  • ⁇ 5> The non-aqueous electrolytic solution according to ⁇ 1> or ⁇ 4>, wherein two of R 1 to R 3 are independently ethenyl groups or ethynyl groups, respectively.
  • ⁇ 6> The non-aqueous compound according to any one of ⁇ 1> to ⁇ 5>, wherein the compound represented by the general formula (1) is at least one selected from the group consisting of the following (1a) to (1e). Electrolyte.
  • ⁇ 7> The non-water according to ⁇ 6>, wherein the compound represented by the general formula (1) is at least one selected from the group consisting of the above (1a), (1b), (1c), and (1d).
  • Electrolyte. ⁇ 8> The non-aqueous according to any one of ⁇ 1> to ⁇ 7>, wherein the borate (B) is at least one selected from the group consisting of lithium tetrafluoroborate and lithium difluorooxalate borate.
  • Electrolyte. ⁇ 9> The non-aqueous electrolytic solution according to any one of ⁇ 1> to ⁇ 8>, wherein the imide salt (C) is bis (fluorosulfonyl) imide lithium.
  • a non-aqueous electrolyte solution capable of achieving a good balance between the effect of reducing the absolute value of internal resistance at a low temperature (0 ° C. or lower, for example, ⁇ 20 ° C.) and the effect of improving the battery capacity after a cycle test Can be provided.
  • the non-aqueous electrolyte solution of the present disclosure is Contains non-aqueous organic solvent, solute, silicon compound (A), borate (B) and imide salt (C)
  • the silicon compound (A) is a compound represented by the following general formula (1).
  • the borate (B) is at least selected from the group consisting of at least one cation selected from the group consisting of alkali metal cations and alkaline earth metal cations, and tetrafluoroborate anion and difluorooxalatoborate anion. It is a borate consisting of a pair with one kind,
  • the imide salt (C) is an imide salt represented by the following general formula (2). It is a non-aqueous electrolyte solution.
  • R 1 to R 3 are substituents having at least one unsaturated bond and an aromatic ring, respectively, and at least one of R 1 to R 3 is a substituent having an aromatic ring. Is. ]
  • Rf 1 and Rf 2 independently represent a fluorine atom or a linear perfluoroalkyl group having 1 to 4 carbon atoms or a branched chain perfluoroalkyl group having 3 to 4 carbon atoms, and M + represents an alkali metal cation.
  • the silicon compound (A) will be described.
  • the silicon compound (A) is also referred to as a component (A).
  • the silicon compound (A) is a compound represented by the following general formula (1).
  • R 1 to R 3 are substituents having at least one unsaturated bond and an aromatic ring, respectively, and at least one of R 1 to R 3 is a substituent having an aromatic ring. Is. ]
  • the carbon number of the substituent having at least one of the unsaturated bond and the aromatic ring represented by R 1 to R 3 is not particularly limited, and examples thereof include a substituent having 2 to 25 carbon atoms, which is preferable. It has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms.
  • the R 1 to R 3 are preferably groups selected from an alkenyl group, an alkynyl group, an aryl group, an alkenyloxy group, an alkynyloxy group, and an aryloxy group.
  • the alkenyl group is preferably a group selected from an ethenyl group and a 2-propenyl group (allyl group), and the alkynyl group is preferably an ethynyl group.
  • the aryl group may be a group selected from a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 4-fluorophenyl group, a 4-tert-butylphenyl group, and a 4-tert-amylphenyl group. preferable.
  • the alkenyloxy group is preferably a group selected from a vinyloxy group and a 2-propenyloxy group (allyloxy group).
  • the alkynyloxy group is preferably a propargyloxy group
  • the aryloxy group is a phenoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, a 4-fluorophenoxy group, a 4-tert-butylphenoxy group, and a 4-tert-. It is preferably a group selected from amylphenoxy groups.
  • R 1 to R 3 is a group selected from the group consisting of an alkenyl group, an alkynyl group, an alkenyloxy group, and an alkynyloxy group. Further, it is preferable that two of R 1 to R 3 are independently ethenyl groups or ethynyl groups from the viewpoint of high durability improving effect. Specific examples thereof include compounds (1a) to (1e) described later.
  • the compound represented by the general formula (1) is preferably at least one selected from the group consisting of (1a) to (1e), among which (1a), (1b), (1c), and (1d). ) Is particularly preferable from the viewpoint of the effect of reducing the absolute value of the internal resistance.
  • the suitable concentration of the silicon compound (A) is not particularly limited with respect to the total amount of the non-aqueous organic solvent and the non-aqueous electrolytic solution containing the solute, but the lower limit is usually 0.01% by mass or more, which is preferable. Is 0.05% by mass or more, more preferably 0.1% by mass or more. In addition, the upper limit is usually 3.0% by mass or less, preferably 2.0% by mass or less, and more preferably 1.0% by mass or less. In addition, one type of silicon compound (A) may be used alone, or a plurality of types may be used in combination.
  • the borate (B) will be described.
  • the borate (B) is also called the component (B).
  • the borate (B) is at least one selected from the group consisting of alkali metal cations and alkaline earth metal cations, and at least one selected from the group consisting of tetrafluoroborate anion and difluorooxalate borate anion.
  • an alkali metal cation is preferable, and among them, lithium ion, sodium ion, or potassium ion is more preferable, and lithium ion is further preferable. That is, the borate (B) is preferably at least one selected from the group consisting of lithium tetrafluoroborate and lithium difluorooxalate borate, and more preferably lithium tetrafluoroborate.
  • the suitable concentration of borate (B) is not particularly limited with respect to the total amount of the non-aqueous organic solvent and the non-aqueous electrolytic solution containing the solute, but the lower limit is usually 0.01% by mass or more. It is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. In addition, the upper limit is usually 9.0% by mass or less, preferably 6.0% by mass or less, and more preferably 3.0% by mass or less. Further, one type of borate (B) may be used alone, or a plurality of types may be used in combination.
  • the imide salt (C) will be described.
  • the imide salt (C) is also called the component (C).
  • the imide salt (C) is an imide salt represented by the following general formula (2).
  • Rf 1 and Rf 2 independently represent a fluorine atom or a linear perfluoroalkyl group having 1 to 4 carbon atoms or a branched chain perfluoroalkyl group having 3 to 4 carbon atoms, and M + represents an alkali metal cation.
  • the alkali metal cation (M + ) constituting the imide salt (C) lithium ion, sodium ion, or potassium ion is more preferable, and lithium ion is further preferable.
  • the anions constituting the imide salt (C) include bis (trifluoromethanesulfonyl) imide anion, bis (pentafluoroethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, and (trifluoromethanesulfonyl) (fluorosulfonyl) imide. It is preferably at least one imide anion selected from the group consisting of anions.
  • the imide salt (C) is preferably bis (fluorosulfonyl) imidelithium.
  • the suitable concentration of the imide salt (C) is not particularly limited with respect to the total amount of the non-aqueous organic solvent and the non-aqueous electrolytic solution containing the solute, but the lower limit is usually 0.01% by mass or more, which is preferable. Is 0.05% by mass or more, more preferably 0.1% by mass or more. In addition, the upper limit is usually 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less. Further, one type of imide salt (C) may be used alone, or a plurality of types may be used in combination.
  • W B / W A is the ratio of the content W B of weight of the mass borate to the content W A of the silicon compound of a non-aqueous electrolyte solution of the present disclosure (A) (B) is 1. It is preferably 5 or more and 3 or less. Further, W C / W A is the ratio of the content of W C of weight of the mass imide salt to the content W A of the silicon compound of a non-aqueous electrolyte solution of the present disclosure (A) (C) is 1 It is preferably 5 or less. Wherein W B / W A, the internal resistance at a low temperature (0 ° C.
  • W C / W A the internal resistance at a low temperature (0 ° C. or less), and, in terms of retention rate of the battery capacity after the cycle test, more preferably 1.5 to 5, 2 to 5
  • W C / W A the internal resistance at a low temperature (0 ° C. or less)
  • retention rate of the battery capacity after the cycle test more preferably 1.5 to 5, 2 to 5
  • W C / W A the internal resistance at a low temperature (0 ° C. or less
  • the solute contained in the non-aqueous electrolytic solution of the present disclosure will be described.
  • the solute is preferably an ionic salt, for example, at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions, hexafluorophosphate anion, trifluoromethanesulfonic acid anion, and fluorosulfone.
  • the cation of the ionic salt which is the solute is lithium, sodium, potassium, or magnesium
  • the anions are hexafluorophosphate anion, trifluoromethanesulfonic acid anion, bis (difluorophosphonyl) imide anion, and (difluorophospho).
  • At least one selected from the group consisting of nyl) (fluorosulfonyl) imide anions is preferable from the viewpoint of high solubility in non-aqueous organic solvents and its electrochemical stability.
  • the preferable concentration of the solute is not particularly limited, but usually, the lower limit is 0.5 mol / L or more, preferably 0.7 mol / L or more, and more preferably 0.9 mol / L or more.
  • the upper limit is usually 2.5 mol / L or less, preferably 2.2 mol / L or less, and more preferably 2.0 mol / L or less.
  • solute may be used alone, or a plurality of types may be used in combination.
  • Non-aqueous organic solvent A non-aqueous organic solvent will be described.
  • the type of the non-aqueous organic solvent used in the non-aqueous electrolytic solution of the present disclosure is not particularly limited, and any non-aqueous organic solvent can be used.
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • methyl propyl carbonate ethyl propyl carbonate
  • Methylbutyl carbonate 2,2,2-trifluoroethylmethyl carbonate
  • 2,2,2-trifluoroethylethyl carbonate 2,2,2-trifluoroethylpropyl carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • the non-aqueous organic solvent contains at least one selected from the group consisting of cyclic carbonate and chain carbonate because it is excellent in cycle characteristics at high temperature. Further, it is preferable that the non-aqueous organic solvent contains an ester because it is excellent in input / output characteristics at a low temperature.
  • the cyclic carbonate include EC, PC, butylene carbonate, FEC, and the like, and at least one selected from the group consisting of EC, PC, and FEC is preferable.
  • chain carbonate examples include EMC, DMC, DEC, methylpropyl carbonate, ethylpropyl carbonate, 2,2,2-trifluoroethylmethyl carbonate, 2,2,2-trifluoroethylethyl carbonate, 1,1, Examples thereof include 1,3,3,3-hexafluoro-1-propylmethyl carbonate and 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate, among which EMC, DMC, DEC, etc. And at least one selected from the group consisting of methylpropyl carbonate.
  • ester examples include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate and the like.
  • the non-aqueous electrolyte solution of the present disclosure may also contain a polymer.
  • Polymers also include what is commonly referred to as polymer solid electrolytes.
  • Polymer solid electrolytes also include those containing a non-aqueous organic solvent as a plasticizer.
  • the polymer is not particularly limited as long as it is an aprotic polymer capable of dissolving the above components (A) to (C), solutes and other additives described below.
  • examples thereof include polymers having a polyethylene oxide in the main chain or side chains, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile and the like.
  • the aprotic non-aqueous organic solvent among the above non-aqueous organic solvents is preferable.
  • the non-aqueous electrolytic solution of the present disclosure may contain at least one of the compounds represented by the following general formulas (3) to (5).
  • X 1 and X 2 each independently represent a halogen atom.
  • a + represents an alkali metal cation, an ammonium ion or an organic cation.
  • X 1 and X 2 each independently represent a halogen atom.
  • the halogen atom represented by X 1 and X 2 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • X 1 and X 2 may be the same or different, but are preferably the same, and both are preferably fluorine atoms.
  • a + represents an alkali metal cation, an ammonium ion or an organic cation.
  • alkali metal cation represented by A + include lithium cation, sodium cation, potassium cation and the like.
  • a + is preferably an alkali metal cation, more preferably a lithium cation.
  • R 4 represents a hydrocarbon group having 2 to 6 carbon atoms.
  • a hetero atom may be contained between the carbon atoms in the hydrocarbon group. Further, any hydrogen atom of the hydrocarbon group may be substituted with a halogen atom.
  • R 4 represents a hydrocarbon group having 2 to 6 carbon atoms.
  • the hydrocarbon group represented by R 4 include a linear or branched alkylene group, an alkenylene group, an alkynylene group and the like.
  • the alkylene group is an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an s-butylene group, a t-butylene group, or an n-pentylene group.
  • -CH 2 CH (C 3 H 7 ) -group n-hexylene group and the like.
  • alkenylene group when R 4 represents an alkenylene group include an ethenylene group and a propenylene group.
  • alkynylene group when R 4 represents an alkynylene group include a propynylene group and the like.
  • the hydrocarbon group represented by R 4 may contain a hetero atom between carbon atoms and carbon atom bonds.
  • the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • any hydrogen atom may be substituted with a halogen atom.
  • the hydrocarbon group in which an arbitrary hydrogen atom is replaced with a fluorine atom include a tetrafluoroethylene group, a 1,2-difluoroethylene group, a 2,2-difluoroethylene group, a fluoroethylene group, and a (trifluoromethyl) ethylene group.
  • a fluorine atom examples include a tetrafluoroethylene group, a 1,2-difluoroethylene group, a 2,2-difluoroethylene group, a fluoroethylene group, and a (trifluoromethyl) ethylene group.
  • R 4 is preferably an unsubstituted alkylene group having 3 to 4 carbon atoms, and more preferably a propylene group.
  • R 5 represents a hydrocarbon group having 2 to 5 carbon atoms.
  • a hetero atom may be contained between the carbon atoms in the hydrocarbon group. Further, any hydrogen atom of the hydrocarbon group may be substituted with a halogen atom.
  • R 5 represents a hydrocarbon group having 2 to 5 carbon atoms.
  • the hydrocarbon group represented by R 5 include a linear or branched alkylene group, an alkenylene group, an alkynylene group and the like.
  • the alkylene group is an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an s-butylene group, a t-butylene group, or an n-pentylene group. , -CH 2 CH (C 3 H 7 ) -group and the like.
  • alkenylene group when R 5 represents an alkenylene group include an ethenylene group and a propenylene group.
  • alkynylene group when R 5 represents an alkynylene group include an ethynylene group and a propynylene group.
  • the hydrocarbon group represented by R 5 may contain a hetero atom between carbon atoms and carbon atom bonds.
  • the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • any hydrogen atom may be substituted with a halogen atom.
  • the hydrocarbon group in which an arbitrary hydrogen atom is replaced with a fluorine atom include a tetrafluoroethylene group, a 1,2-difluoroethylene group, a 2,2-difluoroethylene group, a fluoroethylene group, and a (trifluoromethyl) ethylene group.
  • a fluorine atom examples include a tetrafluoroethylene group, a 1,2-difluoroethylene group, a 2,2-difluoroethylene group, a fluoroethylene group, and a (trifluoromethyl) ethylene group.
  • R 5 is preferably an unsubstituted alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group.
  • LDFBOP lithium difluorobis
  • LTFOP lithium tetrafluorooxalatrate
  • LEFP lithium ethylfluorophosphate
  • ESF ethensulfonylfluoride
  • TSF trifluoromethanesulfonylfluoride
  • MSF Methansulfonyl fluoride
  • PDFP phenyl difluorophosphate
  • overcharge prevention effect a negative electrode film forming effect
  • positive electrode protection effect examples include compounds.
  • the content of the other additive in the non-aqueous electrolytic solution is not particularly limited, but is preferably 0.01% by mass or more and 8.00% by mass or less with respect to the total amount of the non-aqueous electrolytic solution.
  • the inclusion of a compound is also mentioned as a preferred embodiment.
  • the above compound is contained, not only the capacity retention rate after a long-term cycle at a higher temperature can be improved and the resistance increase at a low temperature after high temperature storage can be suppressed, and further, when a Ni-containing electrode is used, an electrolytic solution is obtained from the electrode. This is preferable from the viewpoint of reducing the elution of the Ni component into the water.
  • the lithium salt of the phosphorus complex having an oxalic acid group is at least one selected from the group consisting of lithium tetrafluorooxalate and lithium difluorobis (oxalate) phosphate
  • the effect of suppressing the elution of the Ni component from the positive electrode is particularly excellent, which is more preferable.
  • non-aqueous electrolyte solution as a pseudo-solid with a gelling agent or a crosslinked polymer, as in the case of using it in a non-aqueous electrolyte battery called a polymer battery.
  • the non-aqueous electrolytic solution of the present disclosure may or may not contain the compound represented by the following general formula (6).
  • the content of the compound represented by the following general formula (6) is Examples thereof include a mode in which the content is less than 0.05% by mass.
  • the non-aqueous electrolytic solution of the present disclosure may not contain a compound represented by the following general formula (6).
  • R 6 to R 8 are substituents each independently having at least one of an unsaturated bond and an aromatic ring.
  • R 6 to R 8 are substituents each independently having at least one of an unsaturated bond and an aromatic ring, and specific examples thereof are described in the above description of R 1 to R 3. Can be mentioned.
  • the method for preparing the non-aqueous electrolyte solution of the present disclosure is not particularly limited.
  • it can be prepared by dissolving the silicon compound (A), borate (B), imide salt (C) and solute in a non-aqueous organic solvent.
  • it is effective to prevent the liquid temperature of the non-aqueous organic solvent from exceeding 40 ° C. from the viewpoint of preventing deterioration of the non-aqueous organic solvent and the solute.
  • the liquid temperature By setting the liquid temperature to 40 ° C.
  • the solute when the solute dissolves, the solute reacts with water in the system and decomposes to suppress the production of free acids such as hydrofluoric acid (HF), resulting in This is because it is possible to suppress the decomposition of the non-aqueous organic solvent. It is also effective to add solutes little by little to dissolve and prepare them from the viewpoint of suppressing the production of free acids such as HF.
  • the solute When the solute is dissolved in the non-aqueous organic solvent, the solute may be dissolved while cooling the non-aqueous organic solvent, and the liquid temperature is not particularly limited, but is preferably ⁇ 20 to 40 ° C., more preferably 0 to 40 ° C.
  • the temperature of the non-aqueous electrolytic solution is controlled to ⁇ 10 ° C. or higher and 40 ° C. or lower. Is preferable.
  • the upper limit of the liquid temperature is more preferably 30 ° C. or lower, and particularly preferably 20 ° C. or lower.
  • the non-aqueous electrolyte solution of the present disclosure can be preferably used for a non-aqueous electrolyte battery (preferably a secondary battery).
  • Non-aqueous electrolyte battery has at least (a) the above-mentioned non-aqueous electrolyte solution of the present disclosure, (b) a positive electrode, and (c) a negative electrode material containing a lithium metal, lithium, sodium, potassium, or magnesium. Includes a negative electrode having at least one selected from the group consisting of possible negative electrode materials. Further, it is preferable to include (d) a separator, an exterior body and the like.
  • the positive electrode preferably contains at least one oxide and / or polyanion compound as the positive electrode active material.
  • the positive electrode active material constituting the positive electrode is not particularly limited as long as it is various materials capable of charging and discharging.
  • the positive electrode active material constituting the positive electrode is not particularly limited as long as it is various materials capable of charging and discharging.
  • (b1) a lithium transition metal composite oxide containing at least one metal of nickel, manganese, and cobalt and having a layered structure
  • (b2) a lithium manganese composite oxide having a spinel structure
  • examples thereof include lithium-containing olivine-type phosphates and (b4) lithium excess layered transition metal oxides having a layered rock salt-type structure containing at least one kind.
  • lithium transition metal composite oxide containing at least one or more metals of nickel, manganese, and cobalt (b1), which is an example of the positive electrode active material, and having a layered structure include lithium-cobalt composite oxide and lithium. ⁇ Nickel composite oxide, lithium nickel cobalt composite oxide, lithium nickel cobalt aluminum composite oxide, lithium cobalt manganese composite oxide, lithium nickel manganese composite oxide, lithium nickel manganese Examples include cobalt composite oxides.
  • some of the transition metal atoms that are the main constituents of these lithium transition metal composite oxides are Al, Ti, V, Cr, Fe, Cu, Zn, Mg, Ga, Zr, Si, B, Ba, Y, Sn. Those substituted with other elements such as may be used.
  • lithium-cobalt composite oxide and the lithium-nickel composite oxide include lithium cobalt oxide (LiCo 0.98 Mg 0.) to which dissimilar elements such as LiCoO 2 , LiNiO 2 and Mg, Zr, Al and Ti are added .
  • 01 Zr 0.01 O 2 LiCo 0.98 Mg 0.01 Al 0.01 O 2 , LiCo 0.975 Mg 0.01 Zr 0.005 Al 0.01 O 2 etc.
  • WO2014 / 034043 Lithium cobalt oxide or the like in which a rare earth compound is adhered to the described surface may be used.
  • WO2014 / 034043 Lithium cobalt oxide or the like in which a rare earth compound is adhered to the described surface may be used.
  • a part of the particle surface of the LiCoO 2 particle powder coated with aluminum oxide may be used.
  • the lithium-nickel-cobalt composite oxide and the lithium-nickel-cobalt-aluminum composite oxide are represented by the general formula [11].
  • M 11 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, and B, a is 0.9 ⁇ a ⁇ 1.2, and b, c. Satisfies the conditions of 0.1 ⁇ b ⁇ 0.3 and 0 ⁇ c ⁇ 0.1.
  • These can be prepared according to, for example, the production method described in JP-A-2009-137834 and the like.
  • LiNi 0.8 Co 0.2 O 2 LiNi 0.85 Co 0.10 Al 0.05 O 2 , LiNi 0.87 Co 0.10 Al 0.03 O 2 , LiNi 0.6.
  • Examples thereof include Co 0.3 Al 0.1 O 2 .
  • lithium-cobalt-manganese composite oxide and the lithium-nickel-manganese composite oxide include LiNi 0.5 Mn 0.5 O 2 and LiCo 0.5 Mn 0.5 O 2 .
  • lithium-nickel-manganese-cobalt composite oxide examples include a lithium-containing composite oxide represented by the general formula [12].
  • M 12 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, B, and Sn
  • d is 0.9 ⁇ d ⁇ 1.2
  • the lithium-nickel-manganese-cobalt composite oxide preferably contains manganese in the range shown in the general formula [12] in order to improve structural stability and improve safety at high temperatures in a lithium secondary battery.
  • those further containing cobalt in the range represented by the general formula [12] are more preferable.
  • lithium manganese composite oxide having a spinel structure examples include a spinel-type lithium manganese composite oxide represented by the general formula [13].
  • M 13 is at least one metal element selected from the group consisting of Ni, Co, Fe, Mg, Cr, Cu, Al and Ti, and j is 1.05 ⁇ j ⁇ 1.15. Yes, and k is 0 ⁇ k ⁇ 0.20.
  • LiMnO 2 , LiMn 2 O 4 , Limn 1.95 Al 0.05 O 4 , Limn 1.9 Al 0.1 O 4 , Limn 1.9 Ni 0.1 O 4 , Limn 1 .5 Ni 0.5 O 4 and the like can be mentioned.
  • M 14 is at least one selected from Co, Ni, Mn, Cu, Zn, Nb, Mg, Al, Ti, W, Zr and Cd, and n is 0 ⁇ n ⁇ 1. is there.
  • LiFePO 4, LiCoPO 4, LiNiPO 4, LiMnPO 4, and among them LiFePO 4 and / or LiMnPO 4 are preferred.
  • Examples of the lithium excess layered transition metal oxide having a layered rock salt type structure (b4), which is an example of the positive electrode active material, include those represented by the general formula [15]. xLiM 15 O 2 ⁇ (1-x) Li 2 M 16 O 3 [15] Wherein [15], x is a number satisfying the 0 ⁇ x ⁇ 1, M 15 is at least one or more metal elements mean oxidation number is 3 +, M 16 is the average oxidation number 4 is at least one metal element is +. In the formula [15], M 15 is one kind of metal element preferably selected from trivalent Mn, Ni, Co, Fe, V, and Cr, but is an equal amount of divalent and tetravalent metals.
  • M 16 is one or more metal elements preferably selected from Mn, Zr, and Ti. Specifically, 0.5 [LiNi 0.5 Mn 0.5 O 2 ], 0.5 [Li 2 MnO 3 ], 0.5 [LiNi 1/3 Co 1/3 Mn 1/3 O 2 ] -0.5 [Li 2 MnO 3 ], 0.5 [LiNi 0.375 Co 0.25 Mn 0.375 O 2 ] -0.5 [Li 2 MnO 3 ], 0.5 [LiNi 0.375 Co 0.125 Fe 0.125 Mn 0.375 O 2 ] ⁇ 0.5 [Li 2 MnO 3 ], 0.45 [LiNi 0.375 Co 0.25 Mn 0.375 O 2 ] ⁇ 0.10 [Li 2 TiO 3 ], 0.45 [Li 2 MnO 3 ] and the like.
  • the positive electrode active material represented by the general formula [15] is known to exhibit a high capacity at a high voltage charge of 4.4 V (Li standard) or higher (for example, US Pat. No. 7,135,252). ..
  • These positive electrode active materials can be prepared according to, for example, the production methods described in JP-A-2008-270201, WO2013 / 118661, JP2013-030284, and the like.
  • the positive electrode active material may contain at least one selected from the above (b1) to (b4) as a main component, but other materials include, for example, FeS 2 , TiS 2 , TiO 2 , and V. 2 O 5, MoO 3, MoS 2 or the like transition elements chalcogenide or polyacetylene, polyparaphenylene, polyaniline, and a conductive polymer such as polypyrrole, activated carbon, a polymer that generates radicals, carbon materials, and the like.
  • the positive electrode has a positive electrode current collector.
  • the positive electrode current collector for example, aluminum, stainless steel, nickel, titanium, alloys thereof, or the like can be used.
  • a positive electrode active material layer is formed on at least one surface of a positive electrode current collector.
  • the positive electrode active material layer is composed of, for example, the above-mentioned positive electrode active material, a binder, and, if necessary, a conductive agent.
  • the binder polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene butadiene rubber (SBR), carboxymethyl cellulose, methyl cellulose, cellulose acetate phthalate, hydroxypropyl methyl cellulose, polyvinyl alcohol And so on.
  • a carbon material such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (granular graphite or flake graphite), fluorinated graphite can be used.
  • acetylene black or Ketjen black having low crystallinity it is preferable to use acetylene black or Ketjen black having low crystallinity.
  • the negative electrode material is not particularly limited, but in the case of a lithium battery and a lithium ion battery, a lithium metal, an alloy of a lithium metal and another metal, an intermetal compound, various carbon materials (artificial graphite, natural graphite, etc.), a metal Oxides, metal nitrides, tin (elemental substance), tin compounds, silicon (elemental substance), silicon compounds, activated carbon, conductive polymers and the like are used.
  • the carbon material includes, for example, graphitized carbon, non-graphitized carbon (hard carbon) having a (002) plane spacing of 0.37 nm or more, and graphite having a (002) plane spacing of 0.34 nm or less. And so on. More specifically, there are pyrolytic carbon, cokes, glassy carbon fiber, calcined organic polymer compound, activated carbon, carbon black and the like. Among these, coke includes pitch coke, needle coke, petroleum coke and the like.
  • the calcined organic polymer compound is a carbonized product obtained by calcining a phenol resin, a furan resin, or the like at an appropriate temperature.
  • the carbon material is preferable because the change in the crystal structure due to the occlusion and release of lithium is very small, so that a high energy density can be obtained and excellent cycle characteristics can be obtained.
  • the shape of the carbon material may be fibrous, spherical, granular or scaly. Further, a graphite material whose surface is coated with amorphous carbon or amorphous carbon is more preferable because the reactivity between the material surface and the non-aqueous electrolytic solution is low.
  • the negative electrode preferably contains at least one type of negative electrode active material.
  • the negative electrode active material constituting the negative electrode can be dope / dedope of lithium ions.
  • (c1) a carbon material having a d-value of the lattice surface (002 surface) of 0.340 nm or less in X-ray diffraction
  • (c2) carbon having a d-value of the lattice surface (002 surface) exceeding 0.340 nm in X-ray diffraction.
  • examples thereof include an alloy with lithium and one containing at least one selected from (c5) lithium titanium oxide.
  • One of these negative electrode active materials can be used alone, and two or more of them can be used in combination.
  • (C1) Carbon material having a d value of 0.340 nm or less on the lattice plane (002 plane) in X-ray diffraction examples include thermally decomposed carbons, coke (for example, pitch coke, needle coke, etc.). Petroleum coke, etc.), graphite, organic polymer compound calcined material (for example, phenol resin, furan resin, etc. fired at an appropriate temperature and carbonized), carbon fiber, activated carbon, etc. are mentioned, and these are graphitized. It may be.
  • the carbon material has a (002) plane spacing (d002) measured by X-ray diffraction method of 0.340 nm or less, and among them, graphite having a true density of 1.70 g / cm 3 or more, or graphite thereof.
  • d002 plane spacing measured by X-ray diffraction method of 0.340 nm or less
  • graphite having a true density of 1.70 g / cm 3 or more, or graphite thereof.
  • a highly crystalline carbon material having similar properties is preferable.
  • Amorphous carbon is mentioned as a carbon material in which the d value of the lattice plane (002 plane) in (c2) X-ray diffraction, which is an example of the negative electrode active material, exceeds 0.340 nm, and this is a high temperature of 2000 ° C. or higher. It is a carbon material whose lamination order hardly changes even if it is heat-treated with.
  • non-graphitized carbon hard carbon
  • Carbotron (registered trademark) P manufactured by Kureha Corporation is a typical example.
  • oxide of one or more metals selected from (c3) Si, Sn, Al examples of the negative electrode active material, include silicon oxide, tin oxide, and the like, which can be doped and dedoped with lithium ions. ..
  • SiO x and the like having a structure in which ultrafine particles of Si are dispersed in SiO 2 . When this material is used as the negative electrode active material, charging and discharging are smoothly performed because Si that reacts with Li is ultrafine particles, while the SiO x particles themselves having the above structure have a small surface area, so that the negative electrode active material layer.
  • the paintability of the composition (paste) for forming the negative electrode mixture and the adhesiveness of the negative electrode mixture layer to the current collector are also good. Since SiO x has a large volume change due to charge and discharge, the capacity can be increased and good charge / discharge cycle characteristics can be achieved by using SiO x and the graphite of the negative electrode active material (c1) in a specific ratio in combination with the negative electrode active material. Can be compatible with.
  • (c4) One or more metals selected from Si, Sn, Al, alloys containing these metals, or alloys of these metals or alloys with lithium examples include silicon, tin, and aluminum. Examples thereof include metals, silicon alloys, tin alloys, aluminum alloys, etc., and materials in which these metals and alloys are alloyed with lithium during charge and discharge can also be used.
  • metal simple substances such as silicon (Si) and tin (Sn) described in WO2004 / 100293 and Japanese Patent Application Laid-Open No. 2008-016424, and the metal alloys thereof.
  • the metal is used for an electrode, it is preferable because it can develop a high charge capacity and the volume expansion / contraction due to charging / discharging is relatively small.
  • these metals are known to exhibit a high charging capacity because they are alloyed with Li during charging when they are used as the negative electrode of a lithium ion secondary battery, which is also preferable.
  • a negative electrode active material formed of silicon pillars having a submicron diameter a negative electrode active material made of fibers composed of silicon, and the like described in WO2004 / 042551, WO2007 / 083155, etc. may be used. ..
  • Examples of the (c5) lithium titanate oxide which is an example of the negative electrode active material include lithium titanate having a spinel structure and lithium titanate having a rams delite structure.
  • Examples of lithium titanate having a spinel structure include Li 4 + ⁇ Ti 5 O 12 ( ⁇ changes within the range of 0 ⁇ ⁇ ⁇ 3 depending on the charge / discharge reaction).
  • the lithium titanate having a rams delite structure for example, Li 2 + ⁇ Ti 3 O 7 ( ⁇ changes within the range of 0 ⁇ ⁇ ⁇ 3 depending on the charge / discharge reaction) can be mentioned.
  • negative electrode active materials can be prepared according to, for example, the production methods described in JP-A-2007-018883, JP-A-2009-176752, and the like.
  • sodium ion secondary battery cations in the non-aqueous electrolyte is sodium mainly hard carbon and TiO 2, V 2 O 5, MoO 3 oxide such like are used as the negative electrode active material.
  • sodium-containing transition metal composite oxides such as NaFeO 2 , NaCrO 2 , NanoNiO 2 , NamnO 2 and NaCoO 2 are used as positive electrode active materials.
  • Substituted with the metal of Na 2 FeP 2 O 7 , NaCo 3 (PO 4 ) 2 P 2 O 7 and other transition metal phosphate compounds, TiS 2 , FeS 2 and other sulfides, or polyacetylene and polypara Conductive polymers such as phenylene, polyaniline, and polypyrrole, activated carbon, radical-generating polymers, carbon materials, and the like are used.
  • the negative electrode has a negative electrode current collector.
  • the negative electrode current collector for example, copper, stainless steel, nickel, titanium, alloys thereof, or the like can be used.
  • a negative electrode active material layer is formed on at least one surface of a negative electrode current collector.
  • the negative electrode active material layer is composed of, for example, the above-mentioned negative electrode active material, a binder, and, if necessary, a conductive agent.
  • the binder polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene butadiene rubber (SBR), carboxymethyl cellulose, methyl cellulose, cellulose acetate phthalate, hydroxypropyl methyl cellulose, polyvinyl alcohol And so on.
  • a carbon material such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (granular graphite or flake graphite), fluorinated graphite can be used.
  • the electrode is obtained, for example, by dispersing and kneading an active material, a binder, and a conductive agent, if necessary, in a solvent such as N-methyl-2-pyrrolidone (NMP) or water in a predetermined blending amount. It can be obtained by applying the paste to a current collector and drying it to form an active material layer. It is preferable that the obtained electrode is compressed by a method such as a roll press to adjust the electrode to an appropriate density.
  • NMP N-methyl-2-pyrrolidone
  • the non-aqueous electrolyte battery may include (d) a separator.
  • a separator for preventing contact between the positive electrode (b) and the negative electrode (c)
  • polyolefins such as polypropylene and polyethylene, and non-woven fabrics and porous sheets made of cellulose, paper, glass fiber and the like are used. These films are preferably microporous so that the non-aqueous electrolytic solution soaks in and ions easily permeate.
  • the polyolefin separator include a film such as a microporous polymer film such as a porous polyolefin film that electrically insulates the positive electrode and the negative electrode and allows lithium ions to permeate.
  • the porous polyethylene film may be used alone, or the porous polyethylene film and the porous polypropylene film may be laminated and used as a multi-layer film. Further, a film obtained by combining a porous polyethylene film and a polypropylene film can be mentioned.
  • a metal can such as a coin type, a cylindrical type, or a square type, or a laminated exterior body can be used.
  • the metal can material include a nickel-plated iron steel plate, a stainless steel plate, a nickel-plated stainless steel plate, aluminum or an alloy thereof, nickel, titanium and the like.
  • the laminated exterior body for example, an aluminum laminated film, a SUS laminated film, a silica-coated polypropylene, a laminated film such as polyethylene, or the like can be used.
  • the configuration of the non-aqueous electrolytic solution battery according to the present embodiment is not particularly limited, but for example, an electrode element in which a positive electrode and a negative electrode are arranged to face each other and a non-aqueous electrolytic solution are contained in an exterior body.
  • the shape of the non-aqueous electrolyte battery is not particularly limited, but an electrochemical device having a shape such as a coin shape, a cylinder shape, a square shape, or an aluminum laminate sheet type can be assembled from each of the above elements.
  • the component (A) was dissolved in a concentration of 0.2% by mass, the component (B) in a concentration of 0.4% by mass, and the component (C) in a concentration of 0.6% by mass with respect to the total amount of the non-aqueous electrolyte solution. ..
  • the liquid temperature was maintained in the range of 20 to 30 ° C.
  • Table 1 shows the preparation conditions for the non-aqueous electrolyte solution. Hereinafter, "-" in all the tables indicates no addition.
  • Non-aqueous electrolyte solution No. 1 except that the component (C) component bis (fluorosulfonyl) imide lithium was not added as shown in Table 1 and the concentration of the component (B) component was changed as shown in Table 1. Similar to 1-1, Comparative Non-Aqueous Electrolyte No. 1-1 to 1-2 were prepared. Table 1 shows the preparation conditions for the non-aqueous electrolyte solution.
  • Comparative non-aqueous electrolyte solution No. (A) Comparative non-aqueous electrolyte solution No. (A), except that 0.3% by mass of the compound represented by the formula (1c) was used instead of the compound represented by the formula (1b) as the component (A). Similar to 1-3, Comparative Electrolyte No. 1-4 were prepared. Table 1 shows the preparation conditions for the non-aqueous electrolyte solution.
  • the content of W B / W A, and the component (A) of the mass which is the ratio of the content W B of mass of (A) (B) component to the content W A of weight of the component for W a and W C / W a is the ratio of the content of W C of weight of the component (C) shown in Table 1.
  • a non-aqueous electrolytic solution battery (test cell) was prepared using LiNi 0.6 Co 0.2 Mn 0.2 O 2 as a positive electrode material and graphite as a negative electrode material.
  • LiNi 0.6 Co 0.2 Mn 0.2 O 2 powder 90% by mass mixed with 5% by mass polyvinylidene fluoride (hereinafter referred to as "PVDF") as a binder and 5% by mass of acetylene black as a conductive material.
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • This paste was applied onto an aluminum foil and dried to obtain a positive electrode body for testing. Further, PVDF of 10% by mass as a binder was mixed with 90% by mass of graphite powder, and NMP was further added to form a slurry. This slurry was applied onto a copper foil and dried at 120 ° C. for 12 hours to prepare a test negative electrode body. Then, a non-aqueous electrolytic solution was impregnated into a polyethylene separator to assemble a 50 mAh cell having an aluminum laminate exterior.
  • each non-aqueous electrolytic solution was divided and compared according to the type of component (A) used, and the non-aqueous electrolytic solution to which component (B) and component (C) were not added, respectively.
  • the volume value after 400 cycles of each experimental example was expressed as a relative value when the reference volume value was set to 100. ..
  • the non-aqueous electrolyte battery using the non-aqueous electrolyte of the present disclosure has the effect of reducing the absolute value of the internal resistance at low temperature and the battery capacity after the cycle test, as compared with the comparative example. It was confirmed that the improvement effect of the above can be exhibited in a well-balanced manner.
  • a non-aqueous electrolyte solution capable of achieving a good balance between the effect of reducing the absolute value of internal resistance at a low temperature (0 ° C. or lower, for example, ⁇ 20 ° C.) and the effect of improving the battery capacity after a cycle test Can be provided.

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